Methods and composition for sequential isolation of rare earth elements

ABSTRACT

Methods and compositions are described in which amine-based compounds are utilized in the recovery of rare earth elements from solution. The rare earth elements are recovered selectively and sequentially.

This application is a continuation in part of U.S. Pat. No. 9,499,181,filed Dec. 4, 2013, which claims priority to U.S. ProvisionalApplication No. 61/797,355 filed on Dec. 4, 2012. This applicationfurther claims priority to U.S. Provisional Patent Application No.62/303252, filed on Mar. 3, 2016. These and all other referencedextrinsic materials are incorporated herein by reference in theirentirety. Where a definition or use of a term in a reference that isincorporated by reference is inconsistent or contrary to the definitionof that term provided herein, the definition of that term providedherein is deemed to be controlling.

FIELD OF THE INVENTION

The field of the invention is hydrometallurgy, particularly as it isrelated to the extraction or recovery of rare earth elements orlanthanides.

BACKGROUND

Rare earth elements, also known as the lanthanide family of elements,are commercially valuable metals that are generally present in lowabundance in commercially accessible ores, and often are often foundwith undesirable contaminating elements (for example, thorium). In atypical process for isolation of a member of the lanthanide family, hotsodium hydroxide at high concentrations is used to generate solublelanthanide hydroxide and thorium hydroxide from ore. The mixture ofhydroxides is then treated with hydrochloric acid to generate lanthanidechlorides, which are soluble and remain in solution, and a sludge ofthorium hydroxide (which has reduced solubility at the altered pH).Unfortunately, this process can leave significant amounts of thorium insolution following acid treatment. Since this element is radioactivesignificant further refinement steps are necessary to assure itsremoval, adding significantly to processing costs. In addition, the useof a strong base at an elevated temperature both presents a hazard toworkers and requires the use of specialized equipment. Thus there is apressing need for efficient, effective, and scalable methods for theisolation of rare earth elements at high purity.

Numerous approaches have been devised to attempt to address theseissues. Hydrometallurgy, or the extraction of metals from ores throughtreatment with lixiviant solutions (i.e. lixiviants) is one approachthat has been used successfully for the isolation of metals from avariety of minerals and other sources. In typical hydrometallurgicalprocesses ore is crushed or pulverized to increase surface area prior toexposure to a lixiviant, which contains compounds that render the metalsoluble in the solution and leave behind undesirable contaminants.Following collection of the solution the metal can be recovered from thesolution by various means, such as by electrodeposition or byprecipitation from the solution. Commercial development ofhydrometallurgical processes, however, is often hindered by the expensesinvolved in production and use of the lixiviant, efficient recovery ofthe desired metal, and difficulties in adapting current commercialplants.

In an approach disclosed in U.S. Pat. No. 5,939,034 (to Virnig andMichael), metals are solubilized in an aqueous lixiviant containingammoniacal thiosulfate and extracted into an immiscible organic phasecontaining guanidyl or quaternary amine compounds. All publicationsidentified herein are incorporated by reference to the same extent as ifeach individual publication or patent application were specifically andindividually indicated to be incorporated by reference. Where adefinition or use of a term in an incorporated reference is inconsistentor contrary to the definition of that term provided herein, thedefinition of that term provided herein applies and the definition ofthat term in the reference does not apply.

Metals are then recovered from the organic phase by electroplating. Asimilar approach is disclosed in U.S. Pat. No. 6,951,960 (to Perraud) inwhich metals are extracted from an aqueous phase into an organic phasethat contains an amine chloride. The organic phase is then contactedwith a chloride-free aqueous phase that extracts metal chlorides fromthe organic phase. Amines are then regenerated in the organic phase byexposure to aqueous hydrochloric acid. Such approaches, however, arehindered by the use of volatile amines in the lixiviant, and necessarilyinvolve the use of expensive and potentially toxic organic solvents.

In a related approach, European Patent Application No. EP1309392 (toKocherginsky and Grischenko) discloses a membrane-based method in whichcopper is initially complexed with ammonia or organic amines. Thecopper:ammonia complexes are captured in an organic phase containedwithin the pores of a porous membrane, and the copper is transferred toan extracting agent held on the opposing side of the membrane. Whilesuch an approach minimizes the use of organic solvent, it requires theuse of complex equipment that is not readily adaptable to currentprocessing facilities. In addition, the capacity of such a process isnecessarily limited by the available surface area of the membrane.

Kodama et al. (Energy 33(2008), 776-784) disclose a method for CO₂capture using calcium silicate (2CaO.SiO₂) and a solution of ammoniumchloride (NH₄Cl). This reaction forms soluble calcium chloride (CaCl₂),which is reacted with carbon dioxide (CO₂) under alkaline conditions toform insoluble calcium carbonate (CaCO₃) that captures CO₂ whilereleasing chloride ions (Cl−). Japanese Patent Application No.2005097072 (to Katsunori and Tateaki) discloses a similar method for CO₂capture, in which ammonium chloride (NH₄Cl) is dissociated into ammoniagas (NH₃) and hydrochloric acid (HCl), the HCl being utilized togenerate calcium chloride (CaCl₂) that is mixed with ammonium hydroxide(NH₄OH) for CO₂ capture. Kodama et al. and Katsunori and Tateaki,however, fail to recognize hydrometallurgical applications of suchreactions, and rare earth elements are not considered. In addition, theloss of highly volatile ammonia during processing results in bothinefficiencies and the need for specialized equipment to reduceenvironmental impact.

International Application WO 2012/055750 (to Tavakkoli et al.) disclosesa method for purifying calcium carbonate (CaCO₃), in which CaCO₃ fromhigh content sources is converted to calcium oxide (CaO) by calcination.The resulting CaO is treated with an ammonium chloride (NH₄Cl) solutionto produce calcium chloride (CaCl₂), which is subsequently reacted withhigh purity carbon dioxide (CO₂) to produce CaCO₃ and NH₄Cl. High purityCaCO₃ is subsequently recovered from the solution by crystallizationusing seed crystals. Tavakkoli et al., however, does not consider rareearth elements, and it is not clear if such an approach can be used withlow content or highly contaminated starting materials. In addition,utilization on a large scale would require capturing or containing thehighly volatile ammonia gas that results from such a process.

Attempts have also been made to recover specific rare earth elementsfrom mixed solutions. U.S. Pat. No. 9,115,419, to Laksmanan et al,describes a process in which a number of rare earth metal species andiron are extracted from an ore using an acidic MgCl₂ lixiviant, withspecific rare earth species being selectively removed from the resultingsolution by extraction with various organic solvents. Such solvents,however, pose a significant environmental hazard, and it is not clear ifspecific rare earth elements can be isolated in a sequential manner.Similarly, United States Patent Application Publication No.2013/0309150, to Takur, describes processes for recovery or rare earthelements from waste phosphors by extraction using a strong acidlixiviant, followed by selective recovery of groups of rare earthelements and certain rare earth elements by organic solvent extraction.In addition to the environmental issues posed by the use of suchsolvents, however, it is not clear if the proposed method can beutilized with more typical raw materials that include a greater numberand wider variety of contaminating materials.

Thus, there is still a need for scalable hydrometallurgical methods thatprovides simple, economical, and selective isolation of rare earthelements.

SUMMARY OF THE INVENTION

The inventive subject matter provides apparatus, systems and methods inwhich hydrometallurgical processes utilizing compounds that containorganic amine cation/counterion anion complexes are used to selectivelyrecover rare earth elements from solution. The organic amine compound(s)is/are selected to provide selective precipitation of salts of rareearth elements. The organic amine cation/counterion anion complexgenerates relatively insoluble rare earth hydroxide as a function of therare earth salt's basicity.

One embodiment of the inventive concept is a method for isolating rareearth metals from a raw material that includes a first rare earth metal,a second rare earth metal, and a contaminant. The first rare earth metaland the second rare earth metal are solvated to provide a first aqueoussolution of the first rare earth metal and the second rare earth metal,leaving an extracted solid raw material. The first aqueous solution isseparated from the extracted raw material, then contacted with a basiccompound. The first rare earth metal has sufficient acidity to form acomplex with this basic compound, however the second rare earth metaldoes not. This forms an insoluble first rare earth metal complex and asecond aqueous solution that includes the second rare earth metal. Thefirst rare earth metal complex is separated from this second aqueoussolution, which is then contacted with a second basic compound. Thesecond rare earth metal has sufficient acidity to form a complex withthis second basic compound and forms an insoluble second rare earthmetal complex and a third aqueous solution, from which the insolublesecond rare earth metal complex can be separated. The first rare earthmetal and the second rare earth metal can be separated from the firstrare earth metal complex and the second rare earth metal complex,respectively.

In some embodiments the raw material can further include a third rareearth metal, and the first solution includes this third rare earthmetal. In such an embodiment the third rare earth metal can havesufficient acidity to form a third rare earth metal complex with thefirst basic compound. In other embodiments the raw material can furtherinclude a fourth rare earth metal that is incorporated into the secondsolution. In such embodiments the fourth rare earth metal can havesufficient acidity to form a fourth rare earth metal complex with thesecond basic compound and insufficient acidity to form a complex withthe first basic compound. In still other embodiments the raw materialincludes a fifth rare earth element, and the second solution includesthe fifth rare earth element. In such an embodiment the second aqueoussolution can be contacted with a third basic compound, where the fifthrare earth element has sufficient acidity to form an insoluble fifthrare earth metal complex with the third basic compound and insufficientacidity to form a complex with either of the first basic compound or thesecond basic compound.

Basic compounds of the inventive concept can include ammonia and othernitrogen-containing organic compounds. Suitable nitrogen-containingorganic compounds include monoethanolamine, diethanolamine,triethanolamine, morpholine, ethylene diamine, diethylenetriamine,triethylenetetramine, methylamine, ethylamine, propylamine,dipropylamines, butylamines, diaminopropane, triethylamine,dimethylamine, trimethylamine, glucosamine or any other amino sugar,chitosan, tetraethylenepentamine, amino acids, polyethyleneimine,spermidine, spermine, putrescine, cadaverine, hexamethylenediamine,tetraethylmethylenediamine, polyethyleneamine, cathine, isopropylamine,polylysine, polyornithine, polyarginine, dendritic polyamines, polyaminoacids, and polymeric or oligomeric materials containing one or more lonepairs of electrons suitable for forming a dative bond to an basicproton.

Various objects, features, aspects and advantages of the inventivesubject matter will become more apparent from the following detaileddescription of preferred embodiments, along with the accompanyingdrawing figures in which like numerals represent like components.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an example of a method of the inventive concept in whichcerium is recovered from a thorium contaminated sample, using an organicamine chloride lixiviant that is regenerated. Individual steps of theexemplary method are designated A, B, C, D, E, and F within the figure.

FIG. 2 schematically depicts a method of the inventive concept, in whicha rare earth elements is recovered from an ore using a lixiviant, whichis regenerated.

FIG. 3 schematically depicts another method of the inventive concept, inwhich different rare earth elements are recovered in a stepwise fashion.

FIG. 4 schematically depicts an alternative embodiment of the inventiveconcept, in which different rare earth elements are recovered in astepwise manner.

FIG. 5: Shows a typical UV-Vis spectrum of PrCl₃ and HoCl₃ solution,compared to individual reference spectra of HoCl₃ and PrCl₃.

FIG. 6: Shows a typical UV-Vis spectrum of filtrate from MEA added to aPrCl₃ and HoCl₃ solution, compared to individual reference spectra ofHoCl₃ and PrCl₃.

FIG. 7: Shows a typical UV-Vis spectrum of PrCl₃ and ErCl₃ solution,compared to individual reference spectra of ErCl₃ and PrCl₃.

FIG. 8: Shows a typical UV-Vis spectrum of filtrate from MEA added to aPrCl₃ and ErCl₃ solution, compared to individual reference spectra ofErCl₃ and PrCl₃.

DETAILED DESCRIPTION

Throughout the following discussion, numerous references will be maderegarding lixiviants. A lixiviant should be understood to be a chemicalentity that has the ability to selectively extract metals or metal ionsfrom inorganic or organic solids in an aqueous or other solvent mixture.Within the context of this patent the term organic amine encompassesammonia and ammonia derivatives in addition to nitrogen containingorganic compounds.

Hydrometallurgical methods, such as leaching, have long been used torecover commercially valuable metals from low yield sources, such asmine tailings. Inventors have discovered a hydrometallurgical method forthe recovery of rare earth elements (i.e. rare earth metals), such asmembers of the lanthanide family, through the use of lixiviants thatinclude organic amines. In addition inventors have determined that suchorganic amine-based lixiviants can be regenerated during and/or afterprocessing, permitting the organic amines to act in a pseudocatalyticmanner . This pseudocatalytic behavior allows the organic amines to beapplied in substoichiometric amounts. In addition, the selectivity ofcertain organic amines can permit stepwise isolation of different rareearth elements from the same sample.

The inventive subject matter provides apparatus, systems and methods inwhich rare earth elements are solvated from a raw material to provide anaqueous solution of rare earth metal ions, including cerium (Ce),dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium(Ho), lanthanum (La), lutetium (Lu), neodymium (Nd), praseodymium (Pr),promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), thulium(Tm), ytterbium (Yb), and yttrium (Y). The solvated rare earth metalions are then sequentially and selectively precipitated from the aqueoussolution. Inefficiencies and manufacturing limitations of prior art rareearth refining are avoided by allowing the selective precipitation ofrare earth elements from the soluble ionic solution. This selectiveprecipitation can be accomplished by sequentially adding a series ofincreasingly basic, soluble compounds to the rare earth mixturesolution. In the process the rare earth metals can be sequentiallyprecipitated, in the order of strongest acidity (as an ion in solution)to weakest. This advantageously provides both separation of rare earthmetals from undesired elements present in the raw material andsegregation of different rare earth metals from one another during theisolation process.

In another embodiment, selective and sequential precipitation of rareearth element ions from solution can be performed by adding a one ormore basic compounds (e.g. nitrogen-containing compounds). A series ofbasic compounds can be used to precipitate selected rare earth elementfrom solution based on their acidity. Similarly, the concentration of asingle basic compound can be adjusted to selectively precipitate rareearth elements from solution on the basis of their acidities. In anotherembodiment the selective precipitation of groups of rare earth elementions can be used to produce different “cuts” or fractions that eachinclude two or more rare earth elements. In preferred embodimentsthorium and other undesirable contaminating materials are not initiallysolvated and therefore do not significantly contaminate rare earth metalpreparations of the instant invention.

In some embodiments, the numbers expressing quantities of ingredients,properties such as concentration, reaction conditions, and so forth,used to describe and claim certain embodiments of the invention are tobe understood as being modified in some instances by the term “about.”Accordingly, in some embodiments, the numerical parameters set forth inthe written description and attached claims are approximations that canvary depending upon the desired properties sought to be obtained by aparticular embodiment. In some embodiments, the numerical parametersshould be construed in light of the number of reported significantdigits and by applying ordinary rounding techniques. Notwithstandingthat the numerical ranges and parameters setting forth the broad scopeof some embodiments of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspracticable. The numerical values presented in some embodiments of theinvention may contain certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.

As used in the description herein and throughout the claims that follow,the meaning of “a,” “an,” and “the” includes plural reference unless thecontext clearly dictates otherwise. Also, as used in the descriptionherein, the meaning of “in” includes “in” and “on” unless the contextclearly dictates otherwise.

The recitation of ranges of values herein is merely intended to serve asa shorthand method of referring individually to each separate valuefalling within the range. Unless otherwise indicated herein, eachindividual value with a range is incorporated into the specification asif it were individually recited herein. Unless the context dictates thecontrary, all ranges set forth herein should be interpreted as beinginclusive of their endpoints and open-ended ranges should be interpretedto include only commercially practical values. Similarly, all lists ofvalues should be considered as inclusive of intermediate values unlessthe context indicates the contrary. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g. “such as”) provided with respectto certain embodiments herein is intended merely to better illuminatethe invention and does not pose a limitation on the scope of theinvention otherwise claimed. No language in the specification should beconstrued as indicating any non-claimed element essential to thepractice of the invention.

The following discussion provides many exemplary embodiments of theinventive subject matter. Although each embodiment represents a singlecombination of inventive elements, the inventive subject matter isconsidered to include all possible combinations of the disclosedelements. Thus if one embodiment comprises elements A, B, and C, and asecond embodiment comprises elements B and D, then the inventive subjectmatter is also considered to include other remaining combinations of A,B, C, or D, even if not explicitly disclosed. Groupings of alternativeelements or embodiments of the invention disclosed herein are not to beconstrued as limitations. Each group member can be referred to andclaimed individually or in any combination with other members of thegroup or other elements found herein. One or more members of a group canbe included in, or deleted from, a group for reasons of convenienceand/or patentability. When any such inclusion or deletion occurs, thespecification is herein deemed to contain the group as modified thusfulfilling the written description of all Markush groups used in theappended claims.

Embodiments of the inventive process can include at least one compoundof the general composition depicted in Compound 1 for use with anysource of material that contains one or more a form(s) of a lanthanidehydroxide forming species, that can be hydrated to form Ln(OH)x or otherhydrated species that would react with lixiviants of the form found inCompound 1. Such hydrated forms may be present in the material as it isobtained from nature or can be introduced by processing (for examplethrough treatment with a base or by oxidation), and can be stable ortransient. Selective extraction of the desired lanthanide can be basedon the presence of a metal hydroxide that has a stronger basicity thanthe organic amine-based lixiviants used in the extraction process. Inaddition, an organic amine based lixiviant and counterion can beselected that permit use of the organic amine in substoichiometricamounts (i.e. as a pseudocatalyst).

Organic amines of the inventive concept have the general formula shownin Compound 1, where N is nitrogen, H is hydrogen, and X is a counterion(i.e. a counter anion).

Ny,R₁,R₂,R₃,H—Xz   Compound 1

Suitable counterions can have a pKa ranging from about 1 to about 7, andcan be any form or combination of atoms or molecules that produce theeffect of a negative charge. Counterions can halides (for examplefluoride, chloride, bromide, and iodide), anions derived from mineralacids (for example nitrate, phosphate, bisulfate, sulfate, silicates,carbonate , and bicarbonate), cations derived from organic acids (forexample carboxylate citrate, malate, acetate, thioacetate, propionateand, lactate), organic molecules or biomolecules (for example acidicproteins or peptides, amino acids, nucleic acids, and fatty acids), andothers (for example zwitterions and basic synthetic polymers). Forexample, ammonium chloride (NH₄Cl) conforms to Compound 1 where there isone nitrogen (N₁), R₁, R₂, and R₃ are hydrogen, and there is one counteranion (X₁), which is chloride (Cl−). Compounds having the generalformula shown in Compound 1 can have a wide range of acidities, and anorganic amine of the inventive concept can be selected on the basis ofits acidity so that it can selectively react with one or more rare earthmetal salts or oxides from a sample containing a mixture of rare earthmetal salts or oxides. Such a compound, when dissolved in water oranother suitable solvent, can (for example) effectively extract the rareearth element cerium presented in the form cerium hydroxide in asuitable sample (e.g. alkaline opened monazite). Equation 1 depicts aprimary chemical reaction in extracting an insoluble lanthanide salt (inthis instance a hydroxide salt) from a matrix using an organic aminecation (OA-H+)/counterion (CI−) complex (OA-H+/CI−) as a lixiviant. Notethat the OA-H+/CI− complex dissociates in water into OA-H+and CI−.

Ln(OH)₃(solid)+3 OA-H+(aq)+3 Cl−(aq)→LnCI₃(aq)+3 OA(aq)+3 H₂O   Equation1

The counterion (CI−) is transferred from the organic amine cation(OA-H+) to the lanthanide salt to form a soluble lanthanide /counterioncomplex (LnCI₃), an uncharged organic amine (OA), and water. Oncesolubilized the lanthanide/counterion complex can be recovered fromsolution by any suitable means. For example, addition of a base thatreacts with the lanthanide/counterion complex to form an insolublelanthanide salt can be used to precipitate the extracted lanthanide fromsupernatant following removal of unreacted material. Alternatively, pHchanges, temperature changes, or evaporation can be used to precipitatethe solubilized lanthanide. In other embodiments, the lanthanide couldbe recovered by electrodeposition processes, such as electrowinning orelectrorefining. In still other embodiments of the inventive concept thesolubilized lanthanide can be recovered by ion exchange, for exampleusing a fixed bed reactor or a fluidized bed reactor with appropriatemedia. It should be appreciated that the process of recovering thelanthanide can be selective, and that such selectivity can be utilizedin the recovery of multiple lanthanides as described below.

The organic amine cation/counterion complex can be produced from theuncharged organic amine to regenerate the OA-H+/CI− lixiviant, forexample using an acid form of the counterion (H-CI), as shown inEquation 2.

OA(aq)+H—CI(aq)→OA-H+(aq)+CI−  Equation 2

In a preferred embodiment of the inventive concept the reactiondescribed in Equation 2 can occur in parallel with the reactiondescribed in Equation 1, for example by the addition of an acid form ofthe counterion (HCl) during the period in which the lixiviant is incontact with the sample.

It should be appreciated that an important feature of this process isthe ability to exploit “chemical gain” through the regeneration of thelixiviant, in which the organic amine acts as a pseudocatalyst. Thispermits the use of substantially less than stoichiometric amounts of thelixiviant to recover all of the extractable active metal species as asoluble salt. Although it is not necessary to use less than thestoichiometric amount of lixiviant, doing so has the technical effectsof reducing the environmental impact of such processes and ofsubstantially reducing expense.

Organic amines suitable for the extraction of rare earth elements (forexample from the ores monazite, bastnasite, xenotime and othermaterials) can have a pKa of about 7 to about 14, and can includeprotonated ammonium salts (i.e. not quaternary). Suitable organic aminescan include ammonia, nitrogen containing organic compounds (for examplemonoethanolamine, diethanolamine, triethanolamine, morpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, methylamine,ethylamine, propylamine, dipropylamines, butylamines, diaminopropane,triethylamine, dimethylamine, and trimethylamine), low molecular weightbiological molecules (for example glucosamine, amino sugars,tetraethylenepentamine, amino acids, polyethyleneimine, spermidine,spermine, putrescine, cadaverine, hexamethylenediamine,tetraethylmethylenediamine, polyethyleneamine, cathine, isopropylamine,and a cationic lipid), biomolecule polymers (for example chitosan,polylysine, polyornithine, polyarginine, a cationic protein or peptide),and others (for example a dendritic polyamine, a polycationic polymericor oligomeric material, and a cationic lipid-like material), orcombinations of these. Such organic amines can range in purity fromabout 50% to about 100%. For example, an organic amine of the inventiveconcept can have a purity of about 50%, about 55%, about 60%, about 65%,about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about97%, about 99%, or about 100%. In a preferred embodiment of theinventive concept the organic amine is supplied at a purity of about 90%to about 100%. It should be appreciated that such organic amines candiffer in their ability to interact with different members of thelanthanide family and with contaminating species, and that suchselectivity can be utilized in the recovery of multiple lanthanides asdescribed below.

Inventors further contemplate that zwitterionic species can be suitablelixiviants, and note that such zwitterionic species can formcation/counterion pairs with two members of the same or of differentmolecular species. Examples include amine containing acids (for exampleamino acids and 3-aminopropanoic acid), chelating agents (for exampleethylenediaminetetraacetic acid and salts thereof, ethylene glycoltetraacetic acid and salts thereof, diethylene triamine pentaacetic acidand salts thereof, and1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid and saltsthereof), and others (for example betaines, ylides, andpolyaminocarboxylic acids).

It is notable that the use of biologically derived organic amines is asustainable practice, and has the beneficial effect of making thisprocess more environmentally sound. In addition, it should beappreciated that some organic amines, such as monoethanolamine, have areduced tendency to volatilize during processing than other organicamines, such as ammonia. In some embodiments of the inventive concept anorganic amine can be a low volatility organic amine (i.e. having a vaporpressure less than or equal to about 1% that of ammonia under processconditions). In other embodiments of the inventive concept an organicamine can be a non-volatile organic amine (i.e. having a vapor pressureless than or equal to about 0.1% that of ammonia under processconditions). Capture and control of such low volatility and non-volatileorganic amines requires relatively little energy and can utilize simpleequipment. This reduces the likelihood of such low volatility andnon-volatile organic amines escaping into the atmosphere andadvantageously reduces the environmental impact of their use.

An example of an application of the inventive concept is in theisolation of insoluble cerium hydroxide from a monzanite ore that alsoincludes an undesirable thorium impurity, using an ammonium chloridelixiviant. Equation 3 represents a reaction that takes place oncontacting a monzanite process mud with an ammonium chloride lixiviant.

Ce(OH)₃(solid)+3 NH₄+(aq)+3 Cl−(aq)→CeCl₃(aq)+3 NH₃(aq)+3 H₂O   Equation3

Cerium is extracted from the ore as soluble cerium chloride (CeCl₃),with the generation of uncharged ammonia (NH₃) and water. The lixiviantis regenerated through the addition of hydrochloric acid (HCl), as shownin Equation 4.

NH₃ (aq)+H+(aq)+Cl−(aq) 4 NH₄+(aq)+Cl−(aq)   Equation 4

Advantageously, lixiviant can be regenerated during the extractionprocess by the addition of HCl. In such a process production of ceriumchloride is controlled by the amount of lixiviant present relative tothe amount of extractable metal ions, and the rate at which hydrochloricacid is added to the system. It should be appreciated that in such aprocess either the organic amine cation (ammonium salt) or theunprotonated organic amine (ammonia) can be used initially. Subsequentlyonce the lixiviant has transferred its anion, fresh acid can be added tosupport the protonation of the organic amine so that further metal saltcan be extracted. Since the protonation of the organic amine occurs inthe solution phase, the reaction rate is much greater than directcontact of acid with solid metal oxide/hydroxide. The regeneratedlixiviant can then undergo selective reaction with rare earth hydroxidesaccording to Equation 3. In such a process cerium salts can beselectively extracted from process muds in a continuous manner via thereactions in Equation 3 and Equation 4 until all the cerium hydroxide isconsumed or the addition of acid is ceased. The extent of reaction canbe characterized conveniently by monitoring the pH of the reactingsolution. Since thorium hydroxide in the process mud is not sufficientlybasic to react with the lixiviant, the cerium hydroxide reactspreferentially and is extracted selectively by the lixiviant. As aresult the thorium remains behind in the process mud.

It should be appreciated that systems, methods, and compositions of theinventive concept can also be used to selectively extract and/or refinea desired rare earth element (such as cerium) from an ore containingother contaminants, for example other rare earth elements. By using thelixiviants described herein, one skilled in the art can exploit thevarying degrees of basicity associated with each rare earth element, andchoose a lixiviant of corresponding acidity to achieve selectiveextraction.

It should be noted that the lixiviant allows for the selectiveextraction of cerium hydroxide in this example because it does not reactwith other metals or metal oxides/hydroxides of lower basicity that arefound in the processing muds and solutions. For example zero valancymetals (M0) are not reactive with the lixiviant, as shown in Equation5).

M0(s) +NH₄+(aq)→NO REACTION   Equation 5

This selectivity is in contrast with prior art methods that do notutilize a lixiviant of the inventive concept, where acid will reactnonselectively with zero valancy metals (Equation 6), cerium hydroxide(Equation 7), and other potential metal oxides/hydroxides, for examplethorium oxide (Equation 8).

2M0(s)+6H+(aq)→2M3+(aq)+3H₂(g)   Equation 6

Ce(OH)₃(s)+3H+(aq)→Ce3+(aq)+3H₂O   Equation 7

ThO₂(s)+4H+(aq)→Th4+(aq)+2H₂O   Equation 8

The use of the lixiviant in this pseudo-catalytic manner, acts as aproton shuttle allowing for the selective reaction with, in this examplebut not limited to, cerium hydroxide.

The soluble cerium salt, for example cerium chloride from Equation 3,and the soluble ammonia from Equation 3 (or soluble ammonium ion if thereaction is metal oxide/hydroxide limited) can easily be separated fromthe insoluble solid residue. Once separated, the soluble aqueousfraction can be used as-is if the target process can tolerate the smallquantity of ammonia or ammonium chloride as a contaminant.Alternatively, the solution can be further processed as needed.

As noted above, in some instances the use of a low volatility and/ornon-volatile lixiviant is desirable. An example of such a process of theinventive concept is the extraction of cerium (Ce) from an ore using anon-volatile organic amine, such as monoethanolamine hydrochloride, asshown in FIG. 1, which depicts a stepwise process with steps designatedA to F. As shown in step A of FIG. 1, a tank 100 or other suitablearrangement includes an aqueous solution of an organic amine 110 (inthis instance monoethanolamine) and a mud or slurry 120 containingcerium hydroxide (Ce(OH)₃), thorium oxide (ThO₂) and thorium hydroxide(Th(OH)₄). The extraction process can be initiated as shown in step B ofFIG. 1 by the addition of an acid form of a counterion 130, in thisinstance hydrochloric acid (HCl), which generates an organic acidcation/counterion pair 140 (in this instance monoethanolaminehydrochloride (MEA+/Cl−)). Monoethanolamine hydrochloride (MEA.HCl,HOC₂H₄NH₃Cl) conforms to Compound 1 as follows: one nitrogen atom (N₁)is bound to one carbon atom (R₁=C₂H₅O) and 3 hydrogen atoms (R₂, R₃ andH), and there is one chloride counteranion (X₁=Cl−). As shown in step Cof FIG. 1 this compound, when dissolved in water or another suitablesolvent, can enter or mix with the mud/slurry and, as shown in step D ofFIG. 1, effectively extract a rare earth hydroxide, for example ceriumhydroxide (Ce(OH)₃), by the formation of a soluble rare earthcation/counterion pair 150 (in this instance, cerium chloride(Ce(Cl)₃)). Equation 9 depicts a critical chemical reaction in such anextraction (in this case cerium, from an alkaline opened mined oresource with significant thorium content). Note that MEA.HCl dissociatesin water into monoethanolammonium cation (HOC₂H₄NH₃+(MEAH+)) andchloride anion (Cl−).

Ce(OH)₃(s)+3 HOC₂H₄NH₃+(aq)+3 Cl−(aq)→CeCl₃(aq)+3 HOC₂H₄NH₂ (aq)+3H₂O(l)   Equation 9

As illustrated in step D of FIG. 1, this process also generates anuncharged organic amine 160, in this instance monoethylamine (MEA). Theorganic amine cation/counterion pair 180 can be regenerated, as shown instep E of FIG. 1, from the reaction products of equation 9 by theaddition of the corresponding acid 170 (in this instance HCl), as shownin Equation 10.

HOC₂H₄NH₂ (aq)+HCl(aq)→HOC₂H₄NH₃+(aq)+Cl−  Equation 10

This process can be repeated, eventually leading to the depletion of therare earth element from the mud or slurry, which retains the unwantedthorium contaminants 180 as shown in step F of FIG. 1.

As in the example utilizing ammonium chloride, this processadvantageously utilizes “chemical gain”, in which the MEA.HCl acts as apseudocatalyst. One can use substantially less than stoichiometricamounts of the lixiviant to recover all of the desired extractableactive metal species as a soluble salt. This has both economic andenvironmental benefits and, additionally, simplifies any necessarysubsequent product purification steps.

The metal salt production is controlled by the amount of lixiviantpresent relative to the amount of extractable metal ions, and the rateof acid added to the system. When first starting the process either theammonium salt or the unprotonated organic amine may first be used.Subsequently once the anion is consumed, fresh acid can be added toprovide protonation of the organic amine so that further metal salt canbe produced. Because the protonation of the organic amine occurs inexclusively in the solution phase, the reaction rate is much greaterthan direct contact of acid with metal oxide. The regenerated lixiviantcan then undergo selective reaction with cerium hydroxide according toEquation 9. In this manner, cerium can selectively be extracted fromwaste material in a continuous manner via the reactions in Equation 9and Equation 10 until all the cerium hydroxide is consumed or additionof acid is ceased.

It should be reiterated that the lixiviant allows for the selectiveextraction of cerium in this example because it does not react withother metals or metal oxides/hydroxides in the monazite process mud slag(e.g. thorium oxide does not react with the lixiviant, see Equation 11).

ThO₂(s)+HOC₂H₄NH₃+(aq)→NO REACTION   Equation 11

Whereas, in the absence of the lixiviant, the acid will reactunselectively with thorium oxide (Equation 8) and cerium hydroxide(Equation 8), as well as other potential metals and metaloxides/hydroxides.

The soluble cerium salt and the soluble MEA from Equation 9 (or solubleMEAH+ if reaction is metal oxide/hydroxide limited) can easily beseparated from the insoluble solid residue. Once separated, the solubleaqueous fraction can used as-is if the target process can withstand thesmall quantity of lixiviant as a contaminant, or the solution can befurthered processed as needed.

The rare earth element containing solution can be concentrated ordiluted to a desired strength as required by the end user.Alternatively, the solution can be boiled down or evaporated completely,leaving a rare earth element chloride and/or various hydrates thereof,depending on how vigorously the mixture is dried. The residual unchargedorganic amine could also be removed by this process and optionallycaptured for reuse. The dried rare earth element chlorides could befurther processed into oxides via thermal oxidation, precipitation withagents such oxalic acid, sodium hydroxide, potassium hydroxide or otherprecipitating agents.

In another embodiment of the inventive concept mixture of rare-earthhydroxides can be extracted for further refinement. In such anembodiment an organic amine lixiviant and reaction conditions can beselected that produce a mixture of rare earth element cation/counterionpairs in solution and leaves undesired contaminants in the insolubleslag. The mixture of rare earth element cation/counterion pairs could beseparated from residual lixiviant by, for example, precipitation with ahydroxide. Alternatively, rare earth element salts could be recovered bydrying or other solvent removal technique. In such an approach arelatively volatile lixiviant (such as, for example, ammonia) can beselected to simplify removal and recovery of the organic amine. The mostbasic rare earth element present (for example, lanthanum hydroxide) canbe selectively extracted by exposing the rare earth element hydroxidemixture precipitate to an amount of a second amine-based lixiviant thatis just acidic enough for the lanthanum to be selectively extracted. Theresulting solution could then be concentrated or diluted to a desiredstrength as required by downstream processes.

There are of course many possible lixiviants of the form of Compound 1,and there are likewise many organic amines and rare earth elementsources. While the examples provided have described the action of twoorganic amine lixiviants (i.e. ammonium chloride and monoethanolaminehydrochloride (a.k.a. monoethanolammonium chloride) with one particularcerium source, (monazite) other examples of process of the inventiveconcept can utilize organic amine cation/counterion pairs such asammonium acetate, monoethanolammonium acetate, ammonium nitrate, ormonoethanolammonium nitrate. Alternatively, biologically derivedlixiviants such as the amino acid glycine (or a salt of itself) or thehydrobromide salt of poly-L-lysine can be used. Similarly, whileexamples note the use of monazite ore, other ores (such as xenotime,euxenite, allanite, loparite, samarskite, aeschynite, fergusonite,parasite, synchisite, tengerite, ancylite, florencite, britholite,thalenite, gadolinite, and eudialyte) are suitable. Alternatively,systems, methods, and compositions of the inventive concept can beutilized to recover rare earth elements from electronic waste, consumerwaste, industrial waste, scrap or other excess materials frommanufacturing processes, or other post-utilization sources. Any sourcethat contains a basic form of a rare earth metal can be suitable. Forexample alkali-processed monazite sands that contain thorium compoundscan be used as a source material in methods of the inventive concept. Inpreferred embodiments the rare earth source is a rare earth hydroxidethat can be separated from a matrix using an acid, for example HCl.

Many rare earth elements on the periodic table can form hydroxides; mostof these have very limited solubility in water. These hydroxides alsohave varying degrees of basicity. While cerium (III) hydroxide asproduced from various mineral sources has been cited as an example thereare many other rare earth elements that form suitable bases in water.Examples of other elements that, in hydroxide form, are suitable for usein systems and methods of the inventive concept include scandium,yttrium, lanthanum, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, and leutetium. Such salts have different basicities, whichcan be paired with organic amine based lixiviants of different aciditiesto provide selective recovery.

It should also be noted that systems, methods, and compositions of theinventive concept are not limited to one metal species being extractedwith one particular lixiviant or set of anions. Multiple metal specieswith various organic amine based lixiviants and various anions (oracids) can be used in sequence or in parallel to extract a particularmixture of metals or to produce a particular mixture of metal salts.

As described above, lixiviants of the inventive concept can be appliedin a variety of methods. Examples of some of these methods are depictedschematically in FIG. 2, FIG. 3, and FIG. 4.

FIG. 2 depicts a method of the inventive process 200 in which a sample210, for example an ore or other source or rare earth metal, is mixedwith a lixiviant 220. The lixiviant can include a solvent and one ormore organic amine species as described above in the form of a cation,coupled with a suitable counterion (for example, chlorine and/or otherhalides). Suitable solvents include any protic or highly polar solvent,or any solvent that can solvate large amounts of rare earth metal salts.In preferred embodiments of the inventive concept the solvent is water,a glycol, or a water/glycol mixture.

The organic amine component of the lixiviant can be chosen based onselectivity, efficiency, or economic considerations. Suitable organicamine species can be described by Compound 1, above. In some embodimentsthe organic amine can be a bromide, chloride, acetate, or nitrate saltof diethanolamine or triethanolamine. In other embodiments the organicamine can be a chloride or acetate salt of an amino acid, for exampleglycine or lysine. In preferred embodiments of the inventive concept theorganic amine can be ammonium chloride or monoethanolamine chloride.Similarly, the concentration of organic amine can be selected foroptimal or improved performance. As noted above the organic amine can beutilized in substoichiometric amounts, however this is not arequirement. For example, a monovalent organic amine can be used atconcentrations and volumes that give about a molar ratio of about 0.01to about 3.05 relative to the amount of available rare earth metal inthe sample. In such an embodiment higher organic amine to rare earthelement molar ratios can be utilized in batch processing operations, inwhich the lixiviant is not constantly regenerated through the additionof acid.

The sample 210 can be treated physically and/or chemically prior tomixing with the lixiviant 220. For example, the components of the sample210 can be reduced in size, for example through milling, grinding,pulverizing, or sifting. In some embodiments components of the samplecan have a mean diameter of about 0.005 mm to about 1 mm after suchprocessing. In other embodiments components of the sample can have amean diameter of about 0.01 mm to about 0.25 mm after such processing.In preferred embodiments of the inventive concept components of thesample can have a mean diameter of about 0.025 mm to about 0.125 mm.Such processes improve the surface area to volume ratio of elements ofthe sample and can serve to increase reaction rates. In some embodimentsa sample can be chemically treated, for example through exposure tostrong bases (such as sodium hydroxide), heating, oxidation, or acombination of these. Such chemical treatments can serve to generaterare earth metal salts (for example, hydroxides or oxides) or to alterthe physical structure of the sample or components of the sample.

On interacting with the lixiviant 220, rare earth elements in the sampleinteract with organic amine cations and counterions to form a solublerare earth element cation/counterion complex that is solubilized in thesupernatant 230, along with an uncharged organic amine. This extractionprocess can be rapid, reaching completion in about 0.5 hours to about 24hours. In preferred embodiments the extraction time is from about 2hours to about 4 hours. The mass ratio of rare earth element to solventcan be adjusted to improve process efficiency. In some embodiments theratio of rare earth element to solvent ratio is about 0.02 to about 0.5.In other embodiments the ratio of rare earth element to solvent is about0.05 to about 0.25. In preferred embodiments of the inventive conceptthe ratio of rare earth element to solvent is about 0.1 to about 0.15.

Other parameters can be adjusted during the extraction process in orderto optimize the selectivity and efficiency of the extraction process,for example temperature and mixing speed. In some embodiments thetemperature during extraction can be from about 0° C. to about 200° C.In other embodiments the temperature during extraction is about 50° C.to about 150° C. In a preferred embodiment of the inventive concept thetemperature during extraction is about 150° C. Similarly, duringextraction the mixture of sample and lixiviant can be stirred at about100 rpm to about 2000 rpm. In preferred embodiments the mixture ofsample and lixiviant can be stirred at about 200 rpm to about 500 rpm.

In the extraction process unwanted contaminants are not solvated by thelixiviant, and remain behind as insoluble material, for example as atreated sample 240 that can be further processed if desired. The pH ofthe lixiviant can change during the extraction process, ranging fromabout pH 6 to about pH 13 at the beginning of the extraction, and fromabout pH 6 to about pH 9 at the end of the extraction process. Such pHchanges can provide an indication of the progress of the reaction, or,alternatively, can be used to indicate a need to regenerate thelixiviant. The supernatant 250 can be separated from the insolublematerials of the treated sample 240 by a variety of processes, includingsettling, filtration, or centrifugation, either alone or in combination.The rare earth cation 260 can be recovered from the supernatant 250 byany suitable means, including electrodeposition, precipitation (forexample, by the addition of a base such as hydroxide), and ion exchange.In a preferred embodiment insoluble materials are removed by filtration.In such embodiments the efficiency of the process can be improved bywashing the filter cake of insoluble material to recover additionallixiviant containing solubilized rare earth elements, however this mustbe weighed against the impact of dilution on subsequent steps. In someembodiments the filter cake is washed with a liquid volume of about 10times the volume of the cake wetness. In other embodiments the filtercake is washed with a liquid volume of about 5 times the volume of thecake wetness. In preferred embodiments the filter cake is washed with aliquid volume of about 3 times the volume of the cake wetness.

The uncharged organic amine remaining in the supernatant 250 can, inturn, be regenerated 270 to form an organic amine cation that can formpart of a lixiviant 220 that can be used in the next cycle of thereaction. For example, if a supernatant 250 is treated with an acidicform of the counterion of the lixiviant 220, the uncharged organic aminecan be converted to an organic amine cation/counterion pair that can beused as a lixiviant 220 in the next application of the method. Inpreferred embodiments of the organic concept, an acidic form of thecounterion can be added to the mixed first supernatant and sample 230 toregenerate the charged organic amine/counterion pair in situ 280. Theacid used for regeneration can be any acid that is able to maintain therare earth salt solubility in the lixiviant, for example HBr, HCl, oracetic acid. In a preferred embodiment the acid is HCl. It should beappreciated that in such an embodiment the organic amine can act as apseudocatalyst, serving to shuttle counterions to rare earth elementcomponents of the sample while not being consumed. This advantageouslypermits the use of the organic amine in substochiometric amountsrelative to the rare earth element content of the sample, which limitsboth the environmental impact of such operations and permitsconsiderable savings in materials.

Other embodiments of the inventive concept can advantageously utilizethe selective complex formation and solubility of components of methodsof the inventive concept to recover different rare earth elements fromthe same sample. One example of such a method is shown in FIG. 3. Asshown, such a method can be a chain of reactions that are, essentially,one or more repetitions of the method shown in FIG. 1 applied to aprogressively depleted sample. In an example of such a method 300, asample 305 and a first lixiviant 310 are brought into contact with eachother. The first lixiviant 310 includes a first organic amine cation anda counterion, and reaction 315 with the sample 305 produces a firstdepleted sample 320 and a first supernatant 325 that includes a firstrare earth cation, a counterion, and an uncharged organic amine. Thefirst depleted sample 320 includes materials that were not reactive withthe first lixiviant, which can include additional rare earth elements,other valuable materials, and unwanted contaminants. It can be separatedfrom the first supernatant 325 by any suitable method, includingsettling, filtration, and centrifugation, either alone or incombination. The first rare earth cation 330 can be recovered from thefirst supernatant 325 by any suitable means, includingelectrodeposition, precipitation (for example, by the addition of a basesuch as hydroxide), and ion exchange. The uncharged first organic amineremaining in the supernatant 325 can, in turn, be regenerated 360 togive a first organic amine cation that can form part of a firstlixiviant 310 that can be used in the next cycle of the reaction. Thefirst depleted sample 320 can, in turn, be contacted 340 with a secondlixiviant 335 that includes a second organic amine cation/counterionpair. Reaction with the first depleted sample 240 produces a seconddepleted sample 350 and a second supernatant 345 that includes a solublesecond rare earth element cation/counterion complex and uncharged secondorganic amine. The second rare earth cation 355 can be recovered fromthe second supernatant 345 by any suitable means, includingprecipitation (for example, by treatment with a base that forms aninsoluble salt), electrodeposition, and/or ion exchange. Unchargedsecond organic amine can be treated 365, for example with an acid formof the counterion, to regenerate the second lixiviant 335. In someembodiments of the inventive concept the second depleted sample 350 issubjected to further rounds of treatment with lixiviants in order torecover additional valuable materials. It should be appreciated that, asdescribed in the process illustrated in FIG. 2, that an acid form of thecounterion can be added to the mixtures of lixiviant and sample toregenerate the first organic amine cation 361, the second organic aminecation 366, or both the first and second organic amine cations 361, 366in situ, permitting them to act as pseudocatalysts and permitting thefirst organic amine, the second organic amine, or both the first andsecond organic amine to be used in substochiometric quantities. Thisadvantageously permits the use of the organic amine in substochiometricamounts relative to the rare earth element content of the sample, whichlimits both the environmental impact of such operations and permitsconsiderable savings in materials.

Another embodiment of the inventive concept that permits recovery of twoor more rare earth elements from a sample is shown in FIG. 4. In such amethod 400 a sample 410 is contacted with a lixiviant 420 that includesa first organic amine cation/counterion pair and a second organic aminecation/counterion pair. This mixture 430 results in a treated sample 450and a first supernatant 440. This first supernatant can include a firstrare earth element cation/counterion pair, a second rare earth elementcation/counterion pair, a first uncharged organic amine, and a seconduncharged organic amine. The first rare earth cation 460 can berecovered from the first supernatant 440 by any suitably selectivemeans, including precipitation with a first precipitant (for example, bytreatment with a base that forms an insoluble salt), electroplating, orion exchange. Recovery of the first rare earth cation 460 from the firstsupernatant 440 yields a second supernatant 470, which includes a secondrare earth element cation/counterion pair, an uncharged first organicamine, and an uncharged second organic amine. The second rare earthcation 480 can be recovered from the second supernatant 470 by anysuitable means, such as precipitation with a second precipitant (forexample, through treatment with additional amounts of a base that formsan insoluble salt), electrodeposition, or ion exchange. Followingextraction of rare earth elements, the second supernatant 470 can betreated (for example, by the addition of an acid form of the counterion)to regenerate the lixiviant 420. In some embodiments of the inventiveconcept the first organic amine and the second organic amine (and theirrespective cations) can be different molecular species with differentacidities and/or specificities for rare earth elements. In otherembodiments of the inventive concept the first organic amine and thesecond organic amine can be the same molecular species, with selectivitybetween the first rare earth element and the second rare earth elementbeing provided by the method used for their recovery from supernatants.For example, in some embodiments the first precipitant and the secondprecipitant are different species that selectively precipitate the firstand second rare earth elements, respectively. Alternatively, in otherembodiments the first precipitant and the second precipitant are thesame species utilized under different conditions, for example atdifferent concentrations and/or temperatures. It should be appreciatedthat, as described in the processes illustrated in FIG. 2 and FIG. 3,that an acid form of the counterion can be added to the mixtures oflixiviant and sample to regenerate the first organic amine cation, thesecond organic amine cation, or both the first and second organic aminecations in situ 495, permitting them to act as pseudocatalysts andpermitting the first organic amine, the second organic amine, or boththe first and second organic amine to be used in substochiometricquantities. This advantageously permits the use of the organic amine insubstochiometric amounts relative to the rare earth element content ofthe sample, which limits both the environmental impact of suchoperations and permits considerable savings in materials.

As described above, the Inventor has found that certain lixiviants canbe used to selectively extract rare earth elements from a mixture ofrare earth hydroxides prepared from or present in an ore and/or causticpreparation. Surprisingly, the Inventor has identified compounds thatreact selectively with the more basic rare earth hydroxides, and fail toreact with less basic rare earth hydroxides. This can be represented by

Equation 111, where the reaction proceeds with an basic compound (L′HX)and the suitably basic rare earth hydroxide (RE_(A)(OH)).

Equation 12 shows the lack of reaction that occurs with a different,less basic rare earth hydroxide (RE_(B)(OH)) that fails to react withthe basic component.

RE_(A)(OH)₃(s)+3 L′HX(aq)→RE_(A)X₃(aq)+3 L(aq)+3 H₂O   Equation 11

RE_(B)(OH)₃(s)+3 L′HX(aq)→NO REACTION   Equation 12

In these and the following equations, the counteranion, X, can be aninorganic or an organic counterion. Examples of suitable counterionsinclude halides (such as F⁻, Cl⁻, etc.), carboxylates, nitrates,sulfates, phosphates, or any other suitable counteranion. The basiccomponent (L) can include at least one atom with a lone pair capable offorming a bond or other strong interaction with a basic proton providedby HX. The basic component can have multiple lone-pair containing atoms,which in turn can complex multiple protons. Suitable basic componentscan be inorganic or organic. In a preferred embodiment the basiccomponent includes nitrogen. Examples of suitable basic componentsinclude ammonia, nitrogen containing organic compounds (for examplemonoethanolamine, diethanolamine, triethanolamine, morpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, methylamine,ethylamine, propylamine, dipropylamines, butylamines, diaminopropane,triethylamine, dimethylamine, and trimethylamine), low molecular weightbiological molecules (for example glucosamine, amino sugars,tetraethylenepentamine, amino acids, polyethyleneimine, spermidine,spermine, putrescine, cadaverine, hexamethylenediamine,tetraethylmethylenediamine, polyethyleneamine, cathine, isopropylamine,and a cationic lipid), biomolecule polymers (for example chitosan,polylysine, polyornithine, polyarginine, a cationic protein or peptide),and others (for example a dendritic polyamine, a polycationic polymericor oligomeric material, and a cationic lipid-like material), orcombinations of these. In preferred embodiments the basic components canbe ethylene diamine dihydrochloride and/or lysine dihydrochloride.Lysine monohydrochloride is an example of a basic component where thereare multiple loan pairs on component L, however in this case, not allare complexed to a proton. In some embodiments a zwitterionic compound(for example, glycine) can be used. In such embodiments the counteranion is part of the molecule L. It should be appreciated that theseexamples should not be limited to singly charged anions. Examples ofsuitable compounds having multiply charged anions include ethylenediamine sulfuric acid, and ammonium sulfate. Similarly, dizwitterions(for example, cystine) can be used in methods of the inventive concept.

Surprisingly, the Inventor has found that a reverse reaction (Equation13), in which a rare earth hydroxide is produced by reaction of asolvated rare earth metal salt with a weak base (L) in the presence ofwater, can occur and can be favorable, as shown in Equation 13.

RE_(B)X₃(aq)+3 L(aq)+3 H₂O→RE_(B)(OH)₃(s)+3 L′HX(aq)   Equation 13

By judicious selection of one or more base compounds, a mixture ofmultiple rare earth metal ions in solution can be separated e.g.individual rare earth elements and/or subgroups of rare earth elementscan be selectively precipitated from the mixture) by using a base (L)that has sufficient basicity to initially precipitate the most basicrare earth metal cation(s), while leaving less basic rare earth metalcations in solution. Following separation of solids containing the mostbasic rare earth metal cation(s) from the solution, the next most basicrare earth metal cation(s) can be precipitated with a base having ahigher basicity, for example one sufficient enough to react with one ormore target rare earth cation(s), yet still weak enough to leave therest in solution. This process can be repeated for any number of rareearth ions in solution until all are separated as desired. It should beappreciated that the base compounds can be selected to selectivelyprecipitate a single rare earth metal cation, two rare earth metalcations, or more than two rare earth metal cations from a group of rareearth metal cations in solution. In a preferred embodiment of theinventive concept the initial aqueous solution containing solvated rareearth element species is generated using a compound that does notsolvate undesired species (for example thorium and/or uranium), whichare thereby retained in extracted raw material solids and do not enterthe downstream rare earth metal isolation process. This advantageouslyeliminates or essentially eliminates contamination of rare earth metalmaterials so prepared by such undesired species.

Examples of suitable weak bases suitable for use in methods of theinventive concept include ammonia and nitrogen-containing organiccompounds such as monoethanolamine, diethanolamine, triethanolamine,morpholine, ethylene diamine, diethylenetriamine, triethylenetetramine,methylamine, ethylamine, propylamine, dipropylamines, butylamines,diaminopropane, triethylamine, dimethylamine, trimethylamine,glucosamine or any other amino sugar, chitosan, tetraethylenepentamine,amino acids, polyethyleneimine, spermidine, spermine, putrescine,cadaverine, hexamethylenediamine, tetraethylmethylenediamine,polyethyleneamine, cathine, isopropylamine, polylysine (D, L, or D/L),polyornithine (D, L, or D/L), polyarginine (D, L, or D/L), dendriticpolyamines, polyamino acids, and/or polymeric or oligomeric materialcontaining one or more lone pairs of electrons suitable for forming adative bond to an basic proton. Such weak bases can be used sequentiallyand/or simultaneously in accordance to the requirements of the desiredseparation.

Suitable sources of rare earth elements include naturally occurringsources (such as ores, minerals, and brines) and man-made sources (suchas industrial, consumer, and electronic waste). In naturally occurringsources include ion absorption clay ores, sea bed mud (for example, seabed mud surrounding hot plumes from hydrothermal vents), xenotime,gadolinite, samarskite, euxenite, fergusonite, yttrotantalite,yttrotungstite, yttrofluorite, thalenite, yttrialite, zircon, eudialyte,bastnäsite, monazite, allanite, loparite, ancylite, parisite,lanthanite, chevkinite, cerite, stillwellite, britholite, fluocerite,and cerianite.

Suitable man-made sources of rare earths can be derived from wasteassociated with the manufacture of items incorporating rare earthelements and/or post-consumer/industrial use waste derived from suchitems. Examples of such items include television displays, consumerelectronics, batteries, LEDs, fluorescent lamps, mercury vapor lamps,magnets, ceramic pigments, polishing compounds, catalytic converters,nuclear fuel rods, and various glasses.

In some embodiments of the inventive concept a source of rare earthelements can be treated prior to sequential extraction of rare earthelements. Such treatments can be mechanical and/or chemical. Examples ofmechanical treatment include re-sizing to reduce particle size, forexample by grinding, milling, or abrasion. Such re-sizing can be used toproduce particulate raw materials having a mean maximum diameter of fromabout 10 μm to about 1 cm. In a preferred embodiment such particulateraw materials have a maximum mean diameter of less than 1 mm. Examplesof chemical treatment include treatments to generate oxides or hydroxidesalts of rare earth elements of the raw material. Such processes includebase treatment (for example with sodium hydroxide and/or calciumhydroxide) and/or calcining.

In some embodiments calcining can be followed by treatment with waterand or basic aqueous solutions. For soluble sources of rare earthelements (for example, brines and/or plume from hydrothermal vents)chemical treatment can be provided to generate a precipitate thatincludes rare earth elements prior to selective extraction as describedabove. Such a precipitate can be used either directly, or can besubjected to mechanical treatment as described following precipitation.Suitable chemical treatments for precipitation of rare earth elementsfrom soluble sources include carbonation (for example, using CO₂,carbonate, and/or bicarbonate) and/or base treatment (for example, usingsodium hydroxide and/or calcium hydroxide).

EXAMPLES

Ho/Pr separation: 200 mg of holmium chloride hexahydrate (527 μmol HoCl₃⁻6H₂O) and 130 mg of praseodymium chloride (526 μmol PrCl₃) weredissolved in 10 g of deionized water. The solution was filtered througha 0.45 μm PTFE filter to remove slight cloudiness. A UV-Vis spectrum wastaken of the solution, confirming the presence of both Ho³⁺and Pr³⁺, ascompared with standards acquired separately (see FIG. 5). 110 mg ofmonoethanolamine (1.8 mmol MEA) was added to the solution withagitation. A precipitate was observed to form immediately. This mixturewas again filtered through a 0.45 μm PTFE filter and the solution phaseanalyzed by UV-Vis. At this point, only Pr³⁺was observable (see FIG. 6).

Er/Pr separation: 200 mg of erbium chloride hexahydrate (524 μmol HoCl₃⁻6H₂O) and 130 mg of praseodymium chloride (526 μmol PrCl₃) weredissolved in 10 g of DI water. The solution was filtered through a 0.45μm PTFE filter to remove slight cloudiness. A UV-Vis spectrum was takenof the solution, confirming the presence of both Er³⁺and Pr³⁺, ascompared with standards acquired separately (see FIG. 7). 110 mg ofmonoethanolamine (1.8 mmol MEA) was added to the solution withagitation. A precipitate was observed to form immediately. This mixturewas again filtered through a 0.45 μm PTFE filter and the solution phaseanalyzed by UV-Vis. At this point, only Pr³⁺was observable (see FIG. 8).

It should be apparent to those skilled in the art that many moremodifications besides those already described are possible withoutdeparting from the inventive concepts herein. The inventive subjectmatter, therefore, is not to be restricted except in the spirit of theappended claims. Moreover, in interpreting both the specification andthe claims, all terms should be interpreted in the broadest possiblemanner consistent with the context. In particular, the terms “comprises”and “comprising” should be interpreted as referring to elements,components, or steps in a non-exclusive manner, indicating that thereferenced elements, components, or steps may be present, or utilized,or combined with other elements, components, or steps that are notexpressly referenced. Where the specification claims refers to at leastone of something selected from the group consisting of A, B, C . . . andN, the text should be interpreted as requiring only one element from thegroup, not A plus N, or B plus N, etc.

What is claimed is:
 1. A method for isolating a rare earth element froma raw material comprising: providing a solid raw material comprising afirst rare earth element, a second rare earth element, and acontaminant; solvating the first rare earth element and the second rareearth element to form a first aqueous solution comprising the first rareearth element and the second rare earth element, and an extracted rawmaterial; separating the first aqueous solution from the extracted rawmaterial; contacting the first aqueous solution with a first basiccompound, wherein the first rare earth element has sufficient acidity toform a complex with the first basic compound and the second rare earthelement has insufficient acidity to form a complex with the first basiccompound, thereby forming a first rare earth element complex and asecond aqueous solution, wherein the second aqueous solution comprisesthe second rare earth element; separating the first rare earth elementcomplex from the second aqueous solution; contacting the second aqueoussolution with a second basic compound, wherein the second rare earthelement has sufficient acidity to form a complex with the second basiccompound, thereby forming a second rare earth element complex and athird aqueous solution.
 2. The method of claim 1, further comprising thestep of recovering the first rare earth element from the first rareearth element complex.
 3. The method of claim 1 or 2, further comprisingthe step of separating the second rare earth element complex from thethird aqueous solution.
 4. The method of claims 1 to 3, furthercomprising the step of separating the second rare earth element from thesecond rare earth element complex.
 5. The method of claims 1 to 4,wherein the raw material further comprises a third rare earth element,and wherein the first solution comprises the third rare earth element.6. The method of claim 5, wherein the third rare earth element hassufficient acidity to form a third rare earth element complex with thefirst basic compound.
 7. The method of claims 1 to 6, wherein the rawmaterial further comprises a fourth rare earth element, and wherein thesecond solution comprises the fourth rare earth element.
 8. The methodof claim 5, wherein the fourth rare earth element has sufficient acidityto form a fourth rare earth element complex with the second basiccompound and insufficient acidity to form a complex with the first basiccompound.
 9. The method of claims 1 to 8, wherein the raw materialcomprises a fifth rare earth element, and wherein the second solutioncomprises the fifth rare earth element.
 10. The method of claim 9,further comprising the step of contacting the second aqueous solutionwith a third basic compound, wherein the fifth rare earth element hassufficient acidity to form a fifth rare earth element complex with thethird basic compound and insufficient acidity to form a complex witheither of the first basic compound and the second basic compound. 11.The method of claims 1 to 10, wherein the first basic compound isselected from the group consisting of ammonia and a nitrogen-containingorganic compound.
 12. The method of claims 1 to 10, wherein the secondbasic compound is selected from the group consisting of ammonia and anitrogen-containing compound.
 13. The method of claim 11 or 12, whereinthe nitrogen-containing organic compound is selected from the groupconsisting of monoethanolamine, diethanolamine, triethanolamine,morpholine, ethylene diamine, diethylenetriamine, triethylenetetramine,methylamine, ethylamine, propylamine, dipropylamines, butylamines,diaminopropane, triethylamine, dimethylamine, trimethylamine,glucosamine or any other amino sugar, chitosan, tetraethylenepentamine,amino acids, polyethyleneimine, spermidine, spermine, putrescine,cadaverine, hexamethylenediamine, tetraethylmethylenediamine,polyethyleneamine, cathine, isopropylamine, polylysine, polyornithine,polyarginine, dendritic polyamines, polyamino acids, and a polymeric oroligomeric material containing one or more lone pairs of electronssuitable for forming a dative bond to an basic proton.